Anthraquinone dyestuffs



pared in various ways, but are advantageously Patented Nov. 19, 1946UNITED STATES- PATENT oFncE AN THRAQUIN ONE DYESTUFFS Joseph B. Dickeyand James G. McNally, Rochester, N. Y., assignors to Eastman KodakCompany, Rochester, N. Y., a corporation of New Jersey No Drawing.Application October 23, 194 Serial No. 507,486

5 Claims. (Cl. 260-376) 2 This invention relates to the manufacture of bp s in t e Starting {iyestufi Include those new anthraquinone dyestufisand to the colorapresent in hydr y lky 91111110 Q pS i511011 as! tionwith such dyestuffs of materials made of or NHCH2CH2OH containingcellulose derivatives. NHCH CHHCH3 We have found that anthraquinonedyestuffs c1- CH 0H containing both a hydroxyalkyl group (or rad- H H OHicle) and a hydroxyalkyl roup (or radicle) esm H CH CH QH terified withan organic acid radicle are especially H 0H) 2 suited for thecoloration. of materials made of p H a I H)Z or containing cellulosederivatives, e; g. organic l0 and V derivatives of cellulose. Such newdyestuffs and ,-N(CH2CH2CH2OH)2 the coloration of materials therewithare set T forth in our copending application Serial No. aswell thehydrpxyalkyl groups i fi 306,200, filed November 25, 1939, now Patenthylmxyalkyl arylamlm gmups Such 6 ,3 8, of which the instant applicationis a l lowmg' 'continuation-in-part.

v NHCH CH CH The dyestuffs of our invention can be pre- 2 2 prepared byesterifying a dyestufi containing two or more hydroxyalkyl groups, undercontrolled NHcHzfilHoHa conditions, so that at least one of the hydroxy-0H alkyl groups remains unesterified. Thus, in a l dyestufl containingtwo hydroxyalkyl radicles,

one hydroxylakyl radicle can be esterified by re- NH TNHCHZCHOHCFOHacting the dyestufi with about one-molecular equivalent of an organicacid anhydride, or an and organic acid halide, or an organic acid (inthis latter case, in the presence of a suitable catalyst), i. e. withabout enough of the organic acid ani l hydridaorganic acid halide ororganic acid to t l other hydroxyalkyl groups may be present esterifysubstantially but one of the hydroxyin groups such 5 the followmg:

alkyl groups. The exact chemical reaction taking place is not known. Theprobabilities are that both hydroxyalkyl groups are esterified to someextent. However, by employing about one molecular equivalent ofesterifying agent, the esterified product consists essentially ofdyestufi wherein but one of the hydroxyalkyl groups is O-CHzCHzOHocnlcnonornon esterified and the other hydroxyalkyl group is E notesterified.

Both aliphatic and aromatic (aryl) esterifying CHz-CH: 0H agents can beemployed. Usually a solvent or NH-CH2CHZ-NHCH2CH2OH diluent medium,nonreactive with the esterifying d agent, is present in the reactionmixture. If an organic acid anhydride or an organic acid halide isemployed as an esterifying agent, the alkyl groups are described in thepriorart. In esterification is advantageously effected in the the caseof. anthraquinone compounds, h dr xypresence of a tertiary amine, suchas pyridine or alkylamino denvatives can be prepared by di t y he t rtiy am n t s to densing a leuco anthraquinone with-a hydroxyfl e With tydrogen halide or the organic alkylamine, such as ethanolamine,diethanola- NHCHzCHrO-QH2CH2OH V The starting dyestuffs containing thehydroxyacid generated during the esterification reaction. mine)propanommine, t h m cyglghex- Still other diluent agents, such asethylene chloanolamine, etc., and oxidizing the resulting leuco ride,dioxane or ethyl acetate, may be present. compound to the non-leucoform. Suitable leuco Illustrative hydroxyalkyl groups which mayanthraquinones include, for example, leuco qui-,

Example 1 0.1 gram mole of 1,4-di-B-hydroxyethylamino arithraquinone isreacted in pyridine with grams of chloroacetic acid.

anthraquinone is obtained and colors cellulose acetate silk blue.

0.1 gram mole of 1,4-di'-.6-hydroxyethylamino anthraquinone cansimilarly be reacted with 0.1 gram mole of propionyl chloride, valericanhydride and caproie anhydride, respectively, to obtain compoundswherein one hydroxyethyl group is convert'ed'to respectively.

Example 2 0.1 gram mole of 1,4di-p-hydroxyethylamino anthraquinone isreacted in pyridine with about 0.1 gram mole (slight excess) of maleicanhydride. A hydroxyethyl group is converted. to

The dye compound obtained colors cellulose acetate silk blue.

0.1 gram mole of 1,4-di-p-hydroxyethylamino anthraquinone can similarlybe reacted with 5 grams of formic acid to convert one of thehydroxyethyl groups to a group. The dye compound obtained colorscellulose acetate silk blue.

Example. 3

16.4 g. (0.05 mole) of IA-di-B-hydroxyethylamino anthraqui-none wereplaced in 185 cc. of ethyl acetate. To the resulting mixture were added5.1 g. (0.05 mole) of acetic anhydride. The resulting mixture wasrefluxed for one hour. The mixture was: then diluted with 11 liters ofwater. The. dye was filtered off and dried in the air; Theyield was 13g; The dye melted'at 170 to 180 C,

4 The dye can be represented by the following formula:

It dyed cellulose acetate silk blue.

Example 4 3.26 g. (0.01- mole) of IA-di-p-hydroxyethylaminoanthraquinone were placed in 50 cc. of ethyl acetate, together with 1.68g. (0.01 mole) of methoxy acetic anhydride. The mixture was refluxed for30 minutes. It was then cooled and diluted with a large quantity ofwater. The dye was filtered ofi and dried in the air. A yield of 3' g.was obtained. The dye can be represented by the following formula:

The dye colored cellulose acetate. silk blue. 1

Example 5 3.26 g. (0.01 mole) of lA-di-p-hydroxyethylamino anthraquinonewere placedin 50 cc. of ethyl acetate together with 1.58 g. (0.01 mole)of butyric anhydride. The mixture was refluxed for 30 minutes. It wasthen cooled. and diluted with a large volume of water. The dye wasfiltered off and dried in the air. Theyield was 3 g. The dye can berepresented by the following formula:

NH-OHz-CHzOH C\ NH-cHPo HT-m-o-mm l i The dye colored cellulose acetatesilk blue.

Example 6' 3.26 g. (0.01 mole) of lA-di-p-hydroxyethylaminoanthraquinone were placed in. 50. cc. of ethyl acetate together with2.26 g... (0 .01 mole). of benzoic anhydride. The mixture wasrefluxedfor 30 minutes. The mixture was then cooled and diluted with alarge volume of aqueous sodium hydroxide (5 per cent byweight). The dyewas filtered off, washed with water and dried. The yield was 3.55 g. Thedye melted in hot water. The dye can be represented by the followingformula: U

b irkorrrc-m-ofi' NH-CHrGHz-O-jiI-Cdis o ltco ored celluloseacetate silkblue-green.

Example 7 2 liters of water. The dye was filtered off, washed with waterand dried in the air. The yield was 3.2 g. The dye can be represented bythe following formula:

Cl) IIIH-GHz-CHr-OH C NH-CHz-OHz-O-(fll-Cdln The dye colored celluloseacetate silk blue.

Example 8 16.3 g. (0.05 mole) of 1,4-di-p-hydroxyethylaminoanthraquinone were placed in 250 cc. of ethyl acetate together with 6.5g. (0.05 mole) of propionic anhydride. The mixture was refluxed for onehour. The mixture was then cooled and diluted with 4 liters of water.The dye was filtered off, washed with water and dried in the air. Theyield was 15.3 g. The dye can be represented by the following formula:

NH-CHFCHPOH The dye colored cellulose acetate silk blue.

Example 9 100 g. (0.31 mole) of 1,4-di-p-hydroxyethylamino anthraquinonewere placed in 500 cc. of dry pyridine. The mixture was heated torefluxing, and 35 g. (0.34 mole) of acetic anhydride were run into themixture over a period of 30 minutes. After the addition of the aceticanhydride, the mixture was refluxed for one hour. The mixture was thencooled and diluted with 10 liters of water. Sodium chloride was added tothe diluted mixture to salt out the dye. The dye was filtered off anddried in the air. The yield was 93 g.

Example 10 l g. of 1-p-hydroxyethylamino-4-p-chloracetoxyethylaminoanthraquinone (obtained according to Example 1) was heated in water forone hour. 1 g. of sodium bicarbonate was then added to the mixture andboiling was continued for .the operation.

three hours.. The resulting mixture was allowed to stand for a period ofabout 12 hours. The dye was then filtered off, washed with cold waterand dried in the air.

The" dye had the following formula:

Example 12 3.26 g. (0.01 mole) of 1,4'-di,3-hydroxyethylaminoanthraquinone were placed in 15 cc. of dry pyridine. To the resultingmixture were added dropwise 2.26 g. (0.01 mole) of benzoic anhydridedissolved in pyridine. The resulting mixture was refluxed for two hours.It was then cooled and diluted with cold water. Sodium chloride wasadded to the diluted mixture to salt out the dye. The dye was filteredoff and dried in the air.

In a manner similar to that illustrated above, still other dyescontaining both a hydroxyalkyl group and a hydroxyalkyl radicleesterified with an organic acid radicle can be prepared.

The dyestuffs may be sulfated so as to convert any alkyl group intosulfo alkyl groups. Sulfation may be effected by treatment with strongsulfuric acid.

The dyestuffs produced according to this invention have valuable dyeingproperties for organic derivatives of cellulose. They are of greatestimportance in the coloration of textile materials containing organicderivatives of cellulose, such as cellulose acetate, cellulosepropionate, or cellulose butyrate. The dyestuffs can also be employed todye cellulose ethers, for example, ethyl or benzyl cellulose. The newdyestuifs may also be employed in the coloration of mixed materialscomprising one or more of the aforesaid esters or ethers in admixturewith other textile fibers, for example wool, silk or other animalfibers, or cotton, regenerated cellulose or other cellulosic materials.Such other fibers may be colored by the same dyestuffs as the celluloseesters and ethers when they possess the requisite aflinity, or they maybe colored in the same or different shades by means of other dyestufis,before, after or simultaneously with the coloration of the celluloseesters or ethers.

The dyes are ordinarily applied to the textile materials in the form ofan aqueous suspension which may be prepared by grinding the dye to apaste in the presence of soap or other suitable dispersing agent, anddispersing the resulting paste in water. Dyeing operations may beconducted at a temperature of to C., but any suitable temperature may beemployed. In accordance with the usual dyeing practice, the material tobe dyed will ordinarily be added to the dye bath at a temperature lowerthan that at which the main portion of the dyeing is to be effected, e.g. a temperature of from 45 to 55 C., following which the temperature ofthe dye bath will be raised to that selected for carrying out Thetemperature at which the dyeing operation is directed will varydepending upon the particular material being dyed. Dispersing orsolubilizing agents that can be employed for preparing suspensions ofthe dyes include soap, sulphoricinoleic acid, salts of sull-position ahydroxyalkylamino group esterified with a lower alkyl monocarboxylicacid radical and in the 4-position a hydroxyalkylamino group. 3. Theanthraquinone dyestuff having the formula:

H N-GHzCH'a--O-(HJCHqCL N-CHzCHzOH H 4. The anthraquinone' dyestuflhaving the formula:

N-CHzCH2OH H JOSEPH B. DICKEY. JAMES G. MCNALLY.

